Phase Separation and d Electronic Orbitals on Cyclic Degradation in Li–Mn–O Compounds: First-Principles Multiscale Modeling and Experimental Observations

A combined study involving experiments and multiscale computational approaches is conducted to propose a theoretical solution for the suppression of the Jahn–Teller distortion which causes severe cyclic degradation. As-synthesized pristine and Al-doped Mn spinel compounds are the focus to understand the mechanism of the cyclic degradation in terms of the Jahn–Teller distortion, and the electrochemical performance of the Al-doped sample shows enhanced cyclic performance compared with that of the pristine one. Considering the electronic structures of the two systems using first-principles calculations, the pristine spinel suffers entirely from the Jahn–Teller distortion by Mn3+, indicating an anisotropic electronic structure, but the Al-doped spinel exhibits an isotropic electronic structure, which means the suppressed Jahn–Teller distortion. A multiscale phase field model in nanodomain shows that the phase separation of the pristine spinel occurs to inactive Li0Mn2O4 (i.e., fully delithiated) gradually during cycles. In contrast, the Al-doped spinel does not show phase separation to an inactive phase. This explains why the Al-doped spinel maintains the capacity of the first charge during the subsequent cycles. On the basis of the mechanistic understanding of the origins and mechanism of the suppression of the Jahn–Teller distortion, fundamental insight for making tremendous cuts in the cyclic degradation could be provided for the Li–Mn–O compounds of Li-ion batteries.